CN102891321B - The lithium primary cell improved - Google Patents
The lithium primary cell improved Download PDFInfo
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- CN102891321B CN102891321B CN201210252148.5A CN201210252148A CN102891321B CN 102891321 B CN102891321 B CN 102891321B CN 201210252148 A CN201210252148 A CN 201210252148A CN 102891321 B CN102891321 B CN 102891321B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/06—Electrodes for primary cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/168—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/50—Methods or arrangements for servicing or maintenance, e.g. for maintaining operating temperature
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Abstract
It relates to electrochemical primary cells, its discharge performance with improvement and/or the reliability under physical damnification and/or partial discharge improved.More specifically, it relates to such galvanic element, it includes the nonaqueous electrolyte of cathode material and the improvement improved, described cathode material comprises the pH adjuster of ferrous disulfide and selection, described nonaqueous electrolyte comprises the organic or inorganic additive of solvent, salt, pH adjuster and selection, and described cathode material and nonaqueous electrolyte improve stability test and discharge performance.
Description
The cross reference of related application
Application claims enjoys in the priority of U.S. Provisional Patent Application that on July 20th, 2011 submits to, serial number is 61/509,689, and the full content of this application is herein incorporated by reference.
Technical field
It relates to the reliability under physical damnification (physicalabuse) and/or partial discharge of electrochemical primary cells, its discharge performance with improvement and/or improvement.More specifically, it relates to such galvanic element, it includes the nonaqueous electrolyte of cathode material and the improvement improving the improvement of stability test and discharge performance, described cathode material comprises the pH adjuster of ferrous disulfide and selection, and described nonaqueous electrolyte comprises the organic or inorganic additive of solvent, salt, pH adjuster and selection.
Background technology
Electrochemical cell (cell) (or set of cells (battery)) is used in various electronic as power supply.Manufacturer is attempting increasing ability and the feature of these electronic equipments always, otherwise this improves the requirement to the set of cells wherein used.But, according to the set of cells cabin in equipment, the size and dimension of the set of cells used in such devices is limited or fixing.As a result, if such as to improve the discharge performance of battery or physical property (such as, anti-leakage or crushing strength), such improvement must flow through makes in battery internal improve or improvement and reach.
Therefore, so far, it is provided that the solution of the battery performance of raising includes, for instance, the physical unit of battery is made improvement.Such as, the size of various battery components or thickness can modify to minimize the thickness of the internal cell volume occupied by shell, sealing member or floss hole the dividing plate (separator) that reduces between anode and negative electrode.Such solution attempts to make to maximize for the internal volume of obtainable battery active material.
To attempt to improve battery performance except the amendment that the physical features of battery is made or as the replacement of the amendment that the physical features of battery is made, can modify to attempt to improve battery performance to the composition (such as anode material, electrolyte and/or cathode material) of various battery components.But also it is realized that occur the electrochemical process in battery or reaction to cause increasing cathode thickness when electric discharge, and with forming product.Additionally, along with the depth of discharge of battery increases, by producing extra product, cause the volume of the increase requiring over the discharging product being incorporated to enough voidages (voidvolume) in battery and be received to increase.
In view of afore-mentioned, it will be recognized that each improvement that battery performance improves that brings in battery design also creates challenge (such as, improving the cathode material composition of the improvement of discharge performance, voidage is had more requirement because product increases by this).Accordingly, there exist the constant demand to the battery design effectively balancing these requirements namely, the sustainable existence demand to optimization output or the battery design of the improvement of discharge performance, internal void volume and other desired physical considerations (such as, crushing strength).
Summary of the invention
Therefore, in simple terms, it relates to electrochemical primary cells, it includes battery case, comprise lithium anode, the negative electrode comprising active material of cathode, described active material of cathode comprises ferrous disulfide and the mixture of the pH adjuster selected from lithium carbonate, sodium silicate, ammonium carbonate and ammonium hydrogen carbonate or its combination, wherein, described mixture has the pH value in the scope of about 5 to about 14, dividing plate, nonaqueous electrolyte and described anode, negative electrode and dividing plate communication it is provided with between described anode and described negative electrode.
The disclosure further relates to the negative electrode used in an electrochemical cell.Described negative electrode comprises active material of cathode, and described material comprises ferrous disulfide and the mixture of the pH adjuster selected from lithium carbonate, sodium silicate, ammonium carbonate and ammonium hydrogen carbonate or its combination, and wherein, described mixture has the pH value in the scope of about 5 to about 14.
The disclosure further relates to electrochemical primary cells, it includes battery case, comprise the anode of lithium, comprise the negative electrode of active material of cathode, described active material of cathode comprises ferrous disulfide, it is provided with dividing plate between described anode and described negative electrode, and nonaqueous electrolyte and described anode, described negative electrode and described dividing plate communication, wherein, described electrolyte comprises solvent, the salt dissolved wherein and pH adjuster, wherein said pH adjuster is (i) selected from ethanolamine, the organic additive of diethanolamine and 2-amino-2-methyl-1-propanol or its combination, or (ii) selected from the inorganic additive of ammonium carbonate and ammonium hydrogen carbonate or its combination.
The disclosure further relates to the nonaqueous electrolyte used in an electrochemical cell.Described nonaqueous electrolyte comprises solvent, the salt dissolved wherein and pH adjuster, wherein said pH adjuster is (i) selected from the organic additive of ethanolamine, diethanolamine and 2-amino-2-methyl-1-propanol or its combination, or (ii) selected from the inorganic additive of ammonium carbonate and ammonium hydrogen carbonate or its combination.
The disclosure further relates to above-mentioned electrochemical primary cells embodiment, and wherein said battery is size AA or AAA.The disclosure further relates to such AA battery, and wherein, this battery has the internal void volume of at least about 32%；Or, the disclosure further relates to such AAA battery, and wherein, this battery has the internal void volume of at least about 33.5%.
The disclosure further relates to said one or multiple electrochemical primary cells embodiment, and wherein, described battery includes positive temperature coefficient (PTC) device, and wherein said device has diameter and is at least about the centrally located hole of 5mm.
The disclosure further relates to said one or multiple electrochemical primary cells embodiment, wherein, described battery includes pad (gasket) material, described gasket material comprises polymeric blend or the copolymer of polypropylene (PP) and ethylene propylene diene monomer (EPDM), and wherein said battery also includes separator material, described separator material comprises polypropylene (PP) or polyethylene (PE) or its combination.
Accompanying drawing explanation
Fig. 1 is the cross sectional representation illustrating the exemplary electrochemical galvanic element that embodiment of the disclosure.
Fig. 2 is the cross sectional representation at the top illustrating the exemplary electrochemical galvanic element that embodiment of the disclosure.
Fig. 3 is the diagram of the exemplary battery of disclosure discharge performance under 1000mA electric current.
Fig. 4 is the diagram of the exemplary battery of disclosure discharge performance under 2000mA electric current.
Fig. 5 is the diagram of the exemplary battery of disclosure discharge performance under 300mA electric current.
Fig. 6 is the exemplary battery electric current at 300mA of the disclosure, the diagram of discharge performance at-20 DEG C.
Fig. 7 is the exemplary battery diagram at 300mA, discharge performance at-40 DEG C of the disclosure.
Fig. 8 is the exemplary battery diagram at 2000mA, discharge performance at 60 DEG C of the disclosure.
Fig. 9 is the diagram of the exemplary battery of the high temperature storage disclosure after week discharge performance under 1000mA or 2000mA discharge current.
Figure 10 is the diagram of the exemplary battery of the high temperature storage disclosure after week discharge performance under 1000mA or 2000mA discharge current.
Figure 11 is the diagram of the exemplary battery of the high temperature storage disclosure after week discharge performance under 1000mA or 2000mA discharge current.
Figure 12 is the graphical representation of exemplary of the impact test that battery of this disclosure performs.
Figure 13 is the cross sectional representation of the battery size of the exemplary battery illustrating the disclosure.
It should be noted that the parts that reference marker instruction corresponding in some figure of accompanying drawing is corresponding.
It is furthermore noted that the design of the parts shown in these figures or purpose that is that configuration is not drawn to and/or that be merely cited for.Therefore, parts design or configuration can from the different preset ranges without deviating from the disclosure described here.Therefore these figure are not construed as restrictive.
Detailed description of the invention
According to the disclosure, it was found that the electrochemical primary cells of a kind of improvement, it is for improving discharge performance and minimizing the failure risk owing to physical damnification and/or partial discharge cause simultaneously.Can be enhanced more specifically, it has been found that tolerate physically impaired ability by the physics and the chemical components that rationally select battery, the discharge performance of battery and battery.Especially, according to the disclosure, the chemical components of the battery being modified includes such as (i) cathode material, it comprises ferrous disulfide and the pH adjuster (being discussed in detail below) selected from specific option list, and/or (ii) nonaqueous electrolyte, it comprises solvent, salt and the organic or inorganic additive (being discussed in detail below) selected from specific option list, it has been observed that these parts improve discharge performance and the stability of battery.Additionally or alternatively, the physical unit of the battery being modified includes such as (i) electrode and/or negative electrode, it has and is designed to make the optimized size of the voidage in battery, and/or the gasket material (ii) improved, more specifically, the polymeric material making pad improved, and/or (iii)) positive temperature coefficient (PTC) device, it has been observed and has improved battery performance, in the safety of improvement of battery, stability or physical property (such as, battery tolerates physically impaired ability).
It should be noted that the electrochemical cell of the disclosure can be configured according to battery design well known in the art, or it is configured to consistent with battery design well known in the art, but the design for discussing in detail herein below improves.Such as, in various embodiments, the electrochemical cell of the disclosure is designed to the specification that is suitable for size AA or AAA set of cells.Therefore, it is however generally that, the exemplary embodiment of the battery of the disclosure can in FIG by example.Specifically, this battery can include top cover 1, PTC device 2, battery case 3, gasket seal (gasket) 4, insulating washer (washer) 5, metal washer 6, exhaust membrane (ventingmembrane) 7, dividing plate 9, negative electrode 8, anode 10, insulative base pad 11, outer casing bottom 12 and contact lid 16.Top cover 1 can include one or more hole 18.Additionally, PTC device 2, insulating washer 5, metal washer 6 with contact lid 16 in each comprise centre bore (being 13,15,14 and 17 respectively).When exhaust membrane 7 breaks, the centre bore 14 on metal washer 6 provides exhaust pathway.The diameter of the centre bore 14 of metal washer 16 can such as less than approximately 5mm.The centre bore of insulating washer 5 is that negative contact (tab) 19 provides entrance passing through.The diameter of the centre bore 15 of insulating washer 5 is different according to different battery design.Except the exception listed in detail in the disclosure, generally speaking, the various parts of electrochemical cell can use material well known in the art and technology to prepare.
A. anode
The anode of the galvanic element of the disclosure comprises active material of positive electrode, and this active material of positive electrode comprises alloy lithium or non-alloyed lithium.Such as, in one embodiment, active material of positive electrode can be the lithium of banding or sheet form.Although the composition of lithium can change, it may be desirable to use the lithium that purity is high in the anode.In an embodiment of the disclosure, anode comprises the lithium of about 99.9%.
In the specific embodiment of the disclosure, anode is alkali metal, and is non-alloyed lithium metal with may desire to.In other embodiments of the disclosure, anode comprises non-alloyed lithium, and this non-alloyed lithium can comprise one or more impurity (such as, copper and/or aluminum) of trace natively.Such as, anode can include about the cupra matter of 0.003 to about 0.005wt.% or the alumina matter of about 0.004 to about 0.006wt.%.
In another embodiment of the disclosure, lithium can be melt into alloy with the metal of about 0.10% to about 0.20%, the such as aluminum of preferably about 0.15%.
In this respect, it should be noted that as used herein, anode " active material " can refer to single compound, this single compound is the part of the exoelectrical reaction at the anode place at battery and contributes to discharge capacity of the cell, including impurity and a small amount of other parts (moiety) being contained therein.Therefore, this phrase does not include comprising or to support the collector body (currentcollector) of active material, contact conductor etc..
In other embodiments of the disclosure, anode can have the collector body from the teeth outwards or within lithium.When collector body is present in anode, any metal in various conducting metal, such as copper can be used, as long as conducting metal is stable at inside battery.
Anode may also include positive contact, and this positive contact can be the known in the art any positive contact providing excellent electric contact for collector body.In a preferred embodiment, positive contact comprises the steel of nickel plating.In a further advantageous embodiment, positive contact comprises pure nickel.
Being further noted that in this article as following, in various embodiments, the size of anode and/or composition can optimised (individually or and cathode combination), in order to reach desired anode to negative electrode overall ratio, and/or to reach desired battery internal void volume.
B. negative electrode
The negative electrode of the disclosure comprises active material of cathode.And active material of cathode comprises ferrous disulfide (such as, Natural pyrite) and one or more additional electrochemical active materials alternatively, described electrochemical active material can be particle form.In another embodiment of the disclosure, active material of cathode is selected from iron sulfide, copper sulfide or has the metal sulfide of the running voltage similar to ferrous disulfide.In a preferred embodiment of the disclosure, the concentration of the ferrous disulfide in active material of cathode is about 88% to about the 98% of the weight of active material of cathode, it is more preferred to about 90 to about 95%, further more preferably about 92%.
In this respect, it is noted that as used herein, negative electrode " active material " can refer to single compound, and this single compound is the part of the exoelectrical reaction at the negative electrode place at battery and contributes to discharge capacity of the cell, including impurity and other parts a small amount of being contained therein.Alternatively, however, it can refer to the mixture (when using different compounds) of compound.Such as, according to the disclosure, active material can be ferrous disulfide (including the various impurity being possibly present therein), or the mixture of one or more other compounds of ferrous disulfide and participation exoelectrical reaction.Therefore, this phrase does not include comprising or to support the collector body of active material, contact conductor etc..
Typically, ferrous disulfide is particle form, and its particle size is optimised according to one or more embodiments of the disclosure, in order to optimization battery performance.Such as, in an embodiment of the disclosure, ferrous disulfide comprise have more than about 20, the granule of the average particle size particle size of 30 or 40 microns.In another embodiment of the disclosure, ferrous disulfide comprises the granule with the average particle size particle size more than about 20 microns and less than approximately 30 microns.In another embodiment of the disclosure, ferrous disulfide comprises the granule with the average particle size particle size more than about 30 microns and less than approximately 40 microns.In another embodiment of the disclosure, iron disulfide particles includes the granule with the bimodal representing fine grained and coarse grained blend or multi-modal distribution.That is, these granules are it may be that such as, have the blend of granule and the granule of the average particle size particle size with more than 20 microns of the average particle size particle size of less than 15 microns.Furthermore, it is possible to select the average particle size particle size according to the ferrous disulfide of the disclosure to pass through to provide enough surface areas to affect high speed (highrate) discharge test.
It is noted that, as used herein, " average particle size particle size " is often referred to the average diameter of the volume distributed median of the sample of the composition that can such as use mode well known in the art (such as, using BeckmanCoulterLS230SeriesLaserDiffractionParticleSizeAna lyzerwithMicroVolumeModule) to measure.Such as, the sample of 1g is weighed, and be placed in the beaker of 25ml, be subsequently adding the deionized water of 10ml and two AerosolOT surfactants (the AerosolOT concentration of 1%).Before then the solution of 1ml be used for measurement, solution is mixed and is disperseed about 5 minutes by sound wave.Generally, 3 parallel measurements average particle size particle size value to obtain tested sample is performed.
It is furthermore noted that method well known in the art can be used to control or reach the average particle size particle size of ferrous disulfide, these methods such as include the wet-grinding technology and relative device of such as medium milling or use the dry mill process of jet mill.
When active material of cathode comprises ferrous disulfide, under room temperature and high storage temperature (such as, being up to about 75 DEG C), the acidity level in negative electrode can affect the stability of lithium electrochemical galvanic element.Otherwise this may result in undesirable reaction of lithium surface, these reactions cause at the air blowing (gassing) of memory period and cell expansion.In order to minimize battery unstability, pH adjuster can be added to active material of cathode.Additionally, pH adjuster can be added in electrolyte solution to improve the stability test after (at such as 60 DEG C) high temperature storage.Store at such a temperature one week and may result in performance reduction.
Therefore, in one or more embodiments of the disclosure, active material of cathode comprises the mixture of ferrous disulfide and pH adjuster.PH adjuster is selected from lithium carbonate, sodium silicate, ammonium carbonate, ammonium hydrogen carbonate, magnesium oxide, calcium oxide or its combination.In a preferred embodiment of the disclosure, pH adjuster selects in lithium carbonate, sodium silicate, ammonium carbonate, ammonium hydrogen carbonate or its combination, more particularly lithium carbonate.
When being present in cathode mix, the pH of pH adjuster amendment mixture.If the pH of cathode mix too sour (such as, pH value arrives about between 4 about 1), battery can become unstable.Advantageously, then, the concentration to be enough revised as by the pH value of cathode mix in the scope of about 5 to about 14, preferably about 7 to about 14, more preferably from about 10 to about 12 is existed by pH adjuster.Therefore typically, the concentration range of pH adjuster can be about 0.5% to about the 6% of the weight of cathode mix, or about 1% to about 4%, it is preferable that about 2%.
In this respect, it is noted that the pH value of the mixture being suspended in such as (a) ferrous disulfide in water or (b) ferrous disulfide and pH adjuster can be determined by the following method: (i) be placed in beaker by not carbonated deionized water；(ii), while stirring water, measure Ph value with pH meter measuring device, and utilize the sodium hydroxide solution of dilution that pH value adjusts the pH value of 6.9 to 7.1 when necessary；(iii) sample (a) ferrous disulfide of 5.0g or the mixture of (b) ferrous disulfide and pH regulator are placed in the beaker of 100ml, and add the water adjusted through pH value of 50ml, and (iv) while sample and water are stirred (enough strong in keep the major part suspension of sample not make water form air pocket), with the interval measurement pH value of every 30 seconds, until it is stable, record the stable pH value pH value as (a) ferrous disulfide or the mixture of (b) ferrous disulfide and pH adjuster compound.
There is additional composition in class in the cathode, and it includes such as adhesive material and conductive material.Preferred adhesive material includes Kynoar (PVDF) and polytetrafluoroethylene (PTFE).Adhesive material can exist with the amount of such as about 1% to about 5% or about 1.5% to about the 4% of the weight of cathode mix, preferably about 2%.
Preferred conductive material for the disclosure includes graphite and acetylene black.Conductive material can with about the 1% of the weight of cathode mix to about 5%, it is preferable that the amount of about 4% exists.In a preferred embodiment of the disclosure, negative electrode comprises the acetylene black of the graphite by about the 1.5% of the weight of cathode mix and about 2.5%.
Negative electrode may also include collector body.In one or more embodiments, this collector body can comprise: lithium is (such as, about 99.4 arrive about 99.5wt.%), copper (such as about 0.001wt.%), manganese (such as about 0.001 arrive about 0.006wt.%), magnesium (such as, about 0.001wt.%), nickel (such as about 0.001 arrives about 0.003wt.%), zinc (such as about 0.014 arrives about 0.019wt.%), the compositions (such as about 0.483 arrives about 0.536wt.%) of titanium (such as about 0.009 arrives about 0.017wt.%) and/or silicon and ferrum or these compositions some combine.
Additionally, negative electrode can include negative contact, and negative contact is such as positioned at the centre (that is, when using gelling volume (jellyroll) technology, with center at a distance of about 1/3) of negative electrode.In one embodiment, negative contact can be soldered to the part of negative electrode, this part can in the edge of negative electrode or intermediate lateral without coating.Additionally, negative electrode may also include more than one in the part laterally not covered by active material of cathode.In a preferred embodiment, negative contact comprises nickel and/or ferrum, for instance rustless steel.
As being hereinafter further noted that, the size of negative electrode and/or composition can be optimised (individually or and anode combination) in various embodiments, in order to reach desired anode to negative electrode overall ratio, and/or to reach desired battery internal void volume.
C. nonaqueous electrolyte
The electrochemical cell of the disclosure also includes nonaqueous electrolyte, itself and anode, negative electrode and the dividing plate communication between anode and negative electrode.As a rule, select the electrolyte preferably comprising favourable electrochemical properties to guarantee the suitable compatibility with high-activity cathode material (such as, lithium) and high-energy-density cathode material (such as, ferrous disulfide).
In this respect, it is noted that typically do not use aqueous electrolyte, because anode material can be enough active in carry out chemical reaction with water.Therefore, as used herein, " non-water " electrolyte be often referred to water concentration lower than about 50ppm, be preferably shorter than about 30ppm(namely, the number of every million parts of total water of electrolytical point) electrolyte.
The electrolyte of the disclosure comprises solvent and is dissolved in solute therein.Although many solvents and solute are well known in the art and generally can be used as the nonaqueous electrolyte in electrochemical primary cells, but preferably the solvent of the disclosure and the particular combination of solute be chosen as provide improve at low temperature (such as, from about-40 DEG C to about 0 DEG C) and high temperature (such as, from about 40 DEG C to about 75 DEG C) stability.In a particular embodiment, properly select suitable solvent disclosed herein and solute, to improve the cryogenic property of electrochemical cell.
In a preferred embodiment of the disclosure, solute includes lithium salts or other suitable salt that can be used in lithium battery, that dissolve in a solvent as known in the art.The suitable lithium salts that can use in the electrolyte includes lithium iodide, lithium nitrate, double; two (fluoroform sulphonyl) imine lithium (" LiTFSI ") and the mixture of two or more thereof.In a specific embodiment of the disclosure, electrolyte includes from about 0.5 to about 1.25M, preferably from the lithium salt of about 0.75 to about 1.0M, and this lithium salts is in specific LiTFSI.In another specific embodiment of the disclosure, electrolyte comprises at least two lithium salts, and the concentration of the first salt (such as LiTFSI) is about 0.15 to about between 0.35M, and the concentration of the second salt (such as LiI) arrives about between 0.85M about 0.65.In the certain preferred embodiment of the disclosure, electrolyte solution comprises the LiI of the LiTFSI and about 0.8M of about 0.2M.In another certain preferred embodiment of the disclosure, electrolyte solution comprises the LiI of the LiTFSI and about 0.6M of about 0.3M.In any one of these combinations or mixture, electrolyte can additionally comprise lithium nitrate.Especially, in a preferred embodiment, electrolyte solution comprises the LiTFSI from about 0.6 to about 0.9M and the lithium nitrate from about 0.02 to about 0.4M, it is preferable that the lithium nitrate of the LiTFSI and about 0.1M of about 0.85M.More specifically, in another preferred embodiment of the disclosure, salt is independent lithium nitrate or the combination of lithium nitrate and other salt at least one.
The selection of the suitable solvent that can use in the electrolyte of the disclosure is at least partly dependent on desired solute, more specifically, and the dissolubility of the desired solute in solvent.Typically, solvent is without acyclic ethers.In a preferred embodiment, solvent is selected from: DOX, propylene carbonate, sulfolane, 3,5-dimethyl are differentThe mixture of azoles and both or more person.In preferred embodiment of the present disclosure, it is different that solvent comprises dioxolanes, sulfolane and 3,5-dimethylRing solvent (cyclicsolvent) mixture of azoles.Dioxolanes, sulfolane and 3,5-dimethyl are differentThe mixture of azoles can comprise the dioxolanes by from about the 60% to about 70% of the volume of electrolyte mixture, preferably about 65%, more preferably about 61%；The sulfolane of from about 30% to about 40%, preferably about 35%, more electedly about 39%；And the 3,5-dimethyl of from about 0.1% to about 0.5% and preferably about 0.2% is differentAzoles.In another preferred embodiment of the disclosure, solvent comprises the mixture of dioxolanes and sulfolane.The mixture of dioxolanes and sulfolane can comprise by from about the 55% to about 70% of the volume of mixture, preferably about 65%, further more preferably about 61% dioxolanes；And from about 30% to about 45%, preferably about 35%, further more preferably about 39% sulfolane.
In order to make battery unstability minimize, pH adjuster can be added directly to electrolyte solution.About electrolyte solution, these additives can be the additive of organic or inorganic.Electrolytical suitable organic additive can be added to and include ethanolamine, diethanolamine and 2-amino-2-methyl-1-propanol.These additives can in electrolyte solution independently or exist with the form of its combination.When there is at least one organic additive in the electrolyte, total additive exists with the amount by about the 0.1% of electrolyte weight to about 2.0%.When there is at least one organic additive in the electrolyte, this electrolytical pH typically from about 5 to about 14, and preferably from about 7 to about 14, it is more preferred to from about 10 to about 12.
Inorganic additive can also be added directly to electrolyte to make battery unstability minimize.These inorganic additives include ammonium carbonate, ammonium hydrogen carbonate or its combination.When there is at least one inorganic additive in the electrolyte, additive exists with the amount by about the 0.1% of electrolyte weight to about 5%.When there is at least one inorganic additive in the electrolyte, electrolytical pH from about 5 to about 14, it is preferable that from about 7 to about 14, it is more preferred to from about 10 to about 12.
In this respect, it is noted that pH value can use mode well known in the art to measure, without deviating from the preset range of the disclosure provided herein.
D. dividing plate
There is provided the dividing plate of the disclosure to keep the physical dielectric separation of negative electrode and anode, and the conveying of the ion that permission is between the two.Additionally, dividing plate is used as electrolytical capillary medium (wickingmedium), and being used as eckband (collar), this eckband prevents fragmented portion (fragmentedportions) and the cathode contacts of anode.Dividing plate can be that any of dividing plate used in the art is without deviating from the scope of the present disclosure.But, in preferred embodiment of the present disclosure, dividing plate comprises polyethylene.In another preferred embodiment of the disclosure, dividing plate comprises polypropylene.In another preferred embodiment of the disclosure, dividing plate comprises the polypropylene-polyethylene-polypropylene of three layers.
E. gasket seal material
The electrochemical cell of the disclosure also includes spacer seal, and it exists to prevent electrolyte leakage.Therefore, generally, the function that the selection of suitable gasket material will be the electrolytical composition to use in the battery at least in part, this spacer seal is made by the material of electrolyte inertia or comprises such material.
In addition, the material that spacer seal is exposed in battery context by the duration tolerance that can continue to extend is made or comprises such material (such as, there is suitable flexibility and the resistance to the cold flow under pressure, thus keeping sufficiently effective sealing under its condition being generally exposed at battery (such as, the storage duration of operating condition and prolongation)).
But, in a preferred embodiment, prepared by the material of the electrolyte absorption that the spacer seal of the disclosure is lost by the battery weight presenting reduction after high temperature storage (such as from about 140 to about 160 °F) and reduced.Especially, in preferred embodiment of the present disclosure, spacer seal is prepared by the material of the copolymer comprising polypropylene and ethylene propylene diene monomer (EPDM).May range from from about 0.9 to 1.0g/cm of the density of this gasket seal material3, it is preferred to about 0.95g/cm3.Additionally, the hot strength of gasket seal material from about 1700psi to about 1800psi, and can be preferably about 1740psi(Yield AcrossFlow(23 DEG C), use mode well known in the art to determine).The percentage elongation of gasket seal material can from about 25% to about 35%, and be preferably about 31%(Yield AcrossFlow(23 DEG C), use mode well known in the art (such as standard method of test ASTMD638) to determine).In another preferred embodiment of the disclosure, pad comprises polypropylene.
F. safety device
In an embodiment of the disclosure, electrochemical cell also includes safety device, for instance positive temperature coefficient (PTC) device, and it is typically found in battery to reduce electric current and to carry out protecting against external short circuit or forced electric discharge.But, according to the disclosure, PTC device can also provide protection in other electrical damage situation specific.Especially, PTC device can work by reaching the design activationary temperature limit electric current of PTC device at electrochemical cell.When PTC device activation, its resistance sharply increases, and corresponding electric current reduces and therefore inner heat reduces.When electrochemical cell and PTC device cool down (such as less than about 60 DEG C), the resistance of PTC device reduces, and consequently allows for set of cells and again discharges.If damage situation continued or again occur, continuation is run multiple cycle by PTC device by this way.PTC device will not ad infinitum reset；But, when it stops do so, PTC device will be in high resistance state.
In an exemplary embodiment of the disclosure, polymeric material is made up or is comprised to PTC device of polymeric material, and this polymeric material comprises the non-conductive crystalline organic polymer substrate being loaded with carbon black granules, and the concentration of carbon black granules is enough to make PTC device conducts.When being in cold or state that is that cooling down, polymer is crystallization；As a result, carbon is forced into the region between crystal, is consequently formed various conductive chain.Owing to PTC device is conduction, it will pass through given electric current, and this is known in the industry as " maintaining electric current (holdcurrent) ".If too many electric current is by PTC device (that is, being known in the industry as " tripping current (tripcurrent) "), PTC device will start heating.Along with PTC device heating, polymer starts to expand, and changes into noncrystalline state from crystalline state.Swelling polymer makes carbon granule separate, and makes conductive path disconnect, so that the resistance of PTC increases.This then PTC device is faster generated heat and more expansion, which further improves resistance.Caused resistance increase has been greatly reduced the electric current in circuit.But, small area analysis continues to flow through PTC device, and is enough to the temperature of PTC is maintained the level that PTC device will be made to be maintained under high resistance state.
In the certain preferred embodiment of the disclosure, PTC device has an endoporus, or more generally, and the radius with the device along circular, the hole being centrally located, the device of this circular has the diameter equal to or more than about 5mm.Additionally, in one or more embodiment, the PTC device of the disclosure has in about 0.1 to the scope of about 0.5mm, is preferably about the thickness of 0.3mm.
G. battery parameter
The reliability being known in the art electrochemical primary cells typically reduces or deterioration after partial discharge.Partial discharge includes making cathode thickness increase and the formation of the discharging product that consumes internal volume so that battery is more sensitive to fault (such as in extruding and impact test (CrushandImpacttest) period) during damage measure due to presenting of such as improving or the tendency experiencing internal electrical short circuit between anode and negative electrode.In order to minimize the failure risk owing to physical damnification and/or partial discharge cause, the anode of the electrochemical cell of the disclosure, negative electrode or both sizes or size are modified to allow sufficient voidage not affect battery performance.
In an exemplary embodiment of the disclosure, battery of lithium-iron disulphide has following total exoelectrical reaction:
Anode 4Li → 4Li++4e
Negative electrodeFeS 2 +4e→Fe+2S -2
Overall 4Li+FeS2→Fe+2Li2S
Therefore, during the partial discharge of battery, the discharging product of formation is Fe and Li2S。
When the partial discharge of battery occurs, cathode coating thickness increases due to the formation of discharging product.Result, the physical damnification of the battery of partial discharge can cause the fault because the short circuit of battery causes, the short circuit of battery be by such as suffer internal temperature raise and electrolyte solvent flame (flaming) after mechanical damage situation bottom electrode between electrical contact and cause.
Therefore, in an embodiment of the disclosure, the battery size of electrochemical cell is selected from size AA and size AAA.Additionally, for the probability reducing or eliminating the fault caused by such as physical damnification, the size of electrode makes the voidage of the battery of AA size more than about 30%, it is preferable that more than about 32%, more preferably from about 34%；And the voidage of the battery of AAA size is more than about 30%, it is preferable that more than about 33.5%, more preferably from about 34%.When the battery of AA and AAA size comprises these voidage amounts, battery has shown that the improvement by conventional physical damage measure.The method of voidage and physical damnification capacity for measuring battery is generally known in the art, such as example further in the example of the disclosure.For example, it is possible to deduct the cumulative volume of electrolyte, negative electrode, anode, positive contact (if existence), negative contact (if existence), dividing plate, insulating tape (if existence) and insulating washer (if existence) based on the actual volume of battery case to calculate the volume percent voids of battery.
About above-mentioned voidage, and at this with reference to Figure 13, it is noted that the battery size of AA or the AAA set of cells of the disclosure has diameter 40 as detailed herein, total height 42, ledge (nubbin) height 44 and ledge diameter 46.For the battery of AA size, diameter 40 is about 13.5 to about 14.5mm；Total height 42 is about 49.5 to about 50.5mm；Ledge height 44 is about 1mm or bigger；And ledge diameter 46 is about 5.5mm or less.For the battery of AAA size, diameter 40 is about 9.5 to about 10.5mm；Total height 42 is about 43.5 to about 44.5mm；Ledge height 44 is about 0.8mm or bigger；And ledge diameter 46 is about 3.8mm or less.Battery size provides space to hold anode, negative electrode, electrolyte, dividing plate, gasket material closed component, collector body and other internal parts that may be present, reserves enough voidages to hold any electrode expansion caused due to electric discharge and any gas and forms (if existence).
As mentioned, one or more embodiments of the disclosure can be revised electrode size, in order to provide enough voidages.Additionally or alternatively, it is noted that changing anode, negative electrode or both sizes can additionally affect the anticathode overall ratio of galvanic anode.Following parameter represents the exemplary embodiment of the battery of the disclosure:
H. manufacture method
The electrochemical primary cells of the disclosure can manufacture without deviating from the scope of the present disclosure in any suitable way known in the art.Suitable technology includes such as " gelling volume " technology, wherein, battery is manufactured: electrode active material applies, dries and be pressed into the opposite major surfaces of the sheet metal being used as collector body by following manner, cut into the banding with preset width and length, and it is spirally wound sheet metal, as anode and negative electrode, and between the anode and cathode dividing plate is set with spiral type.After the battery case being inserted into electrode assemblie, nonaqueous electrolyte is added to battery.Then method well known in the art and parts (including the gasket seal material and/or the PTC device that describe in detail in this article more than using in one or more specific embodiments) can be used in battery case by anode, negative electrode, dividing plate and electrolyte sealability.In one embodiment of the invention, battery is manufactured to the additional cathode material allowing to be positioned at gelling volume center and forms stone.In another embodiment of the disclosure, manufacture method includes increasing to axle diameter about 3.5mm, which in turns increases the voidage of battery.
-----
Example below describes the various embodiments of the disclosure.Considering explanation or the practice of the disclosure described herein, other embodiments within the scope of the appended claims will become apparent to those skilled in the art.Description is intended to be to be considered merely as exemplary together with example, and the scope of the present disclosure and spirit are indicated by the claims after example.
Example
There is provided following limiting examples with the example disclosure further.
In example 1-9, test 5 different batteries.Test section (testlot) 45 is the control zone (controllot) comprising electrolyte #45.Electrolyte #45 comprises following ingredients: 1,2-dimethoxy-ethane (about 16%v/v)；1,3-dioxolanes (about 58%v/v)；Diethylene glycol dimethyl ether (about 12%v/v)；Lithium iodide (from about 9.5 to about 15wt.%)；LiTFSI(is less than approximately 10wt.%)；3,5-dimethyl is differentAzoles (about 0.2%v/v), lithium nitrate (less than approximately 5wt.%)；And the water less than approximately 50ppm.
The electrolyte of test section 113 comprises 1MLiTFSI, by the v/v(volume by volume of 65:35) DOX and to have trace (0.2vol.%) 3,5-dimethyl differentThe solvent mixture of the sulfolane of azoles and the water less than approximately 50ppm.
The electrolyte of test section 114 comprises 1M(LiTFSI:LiI=1:2), by the v/v(volume by volume of 65:35) DOX and to have trace (0.2vol.%) 3,5-dimethyl differentThe solvent mixture of the sulfolane of azoles and the water less than approximately 50ppm.
The electrolyte of test section 115 comprises 1M(LiTFSI:LiI=1:4), by the v/v(volume by volume of 65:35) DOX and to have trace (0.2vol.%) 3,5-dimethyl differentThe solvent mixture of the sulfolane of azoles and the water less than approximately 50ppm.
The electrolyte of test section 116 comprises 1M(LiTFSI:LiI=1:4), by the v/v(volume by volume of 55:45) DOX and to have trace (0.2vol.%) 3,5-dimethyl differentThe solvent mixture of the sulfolane of azoles and the water less than approximately 50ppm.
The electrolyte of test section 117 comprises 1MLiTFSI(22.3wt.%), by the v/v(volume by volume of 61:39) DOX (47.3wt.%) and to have trace (0.2vol.%) 3,5-dimethyl differentThe solvent mixture of the sulfolane (30.2wt.%) of azoles and the water less than approximately 50ppm.
The electrolyte of test section 118 comprises 0.88MLiTFSI(19.7wt.%), by the v/v(volume by volume of 61:39) DOX (48.9wt.%) and to have trace (0.2vol.%) 3,5-dimethyl differentThe solvent mixture of the sulfolane (31.2wt.%) of azoles and the water less than approximately 50ppm.
In each test section (including control zone #45), lithium carbonate is involved in the cathode, and measures the discharge performance of each test section at different temperature and electric current.In each figure, discharge performance is measured by the cell voltage (V) within discharge time (minute) or (second) or (mV).
Example 1
Fig. 3 illustrates the LFBAA size battery group (Li-FeS comprising five kinds of electrolyte and lithium carbonate2AA set of cells) discharge performance.Discharge performance is at room temperature to measure under the electric current of 1000mA.As it is shown on figure 3, electrolyte 113(comprises 1MLiTFSI, DXL:SUL65:35 (v/v)) show the battery weight loss of the most long discharge time under ceiling voltage and reduction, in the disclosure, other places are discussed.
Example 2
Fig. 4 illustrates the discharge performance of the LFBAA set of cells comprising five kinds of electrolyte and lithium carbonate.Discharge performance is at room temperature measured under 2000mA electric current.As shown in Figure 4, although electrolyte shows similar discharge performance, electrolyte 113,114 and 116 better than electrolyte 115 performance.
Example 3
Fig. 5 illustrates the discharge performance of the LFBAA set of cells comprising five kinds of electrolyte and lithium carbonate.Discharge performance is at room temperature measured under 300mA discharge current.As it is shown in figure 5, test electrolyte 113,114,115 and 116 shows that ratio controls the discharge performance that electrolyte 45 improves.
Example 4
Fig. 6 illustrates the discharge performance of the LFBAA set of cells comprising five kinds of electrolyte and lithium carbonate.Discharge performance is measured under 300mA discharge current at-20 DEG C.
Example 5
Fig. 7 illustrates the discharge performance of the LFBAA set of cells comprising five kinds of electrolyte and lithium carbonate.Discharge performance is measured under 300mA electric current at-40 DEG C.As it is shown in fig. 7, electrolyte 113 and 115 shows discharge performance best under this low temperature.
Example 6
Fig. 8 illustrates the discharge performance of the LFBAA set of cells comprising five kinds of electrolyte and lithium carbonate.Discharge performance is measured under 2000mA electric current at 60 DEG C.As shown in Figure 8, electrolyte shows similar discharge performance；But, electrolyte 114 and 116 shows the discharge performance of the best.
Example 7
Fig. 9 illustrates that the electrolyte 113 with lithium carbonate at high temperature (60 DEG C) stores the discharge performance after a week.As it is shown in figure 9, under the discharge current of 1000mA or 2000mA, the set of cells comprising electrolyte 113 and lithium carbonate all show almost identical discharge performance under fresh state and after at high temperature storing one week.
Example 8
Figure 10 illustrates that the electrolyte 114 with lithium carbonate stores the discharge performance after a week under high temperature (60 DEG C).As shown in Figure 10, under the discharge current of 1000mA or 2000mA, the set of cells comprising electrolyte 114 and lithium carbonate all show almost identical discharge performance under fresh state and after at high temperature storing one week.
Example 9
Figure 11 illustrates that the electrolyte 115 with lithium carbonate stores the discharge performance after a week under high temperature (60 DEG C).As shown in figure 11, under the discharge current of 1000mA or 2000mA, the set of cells comprising electrolyte 115 and lithium carbonate all show almost identical discharge performance under fresh state and after at high temperature storing one week.
Example 10
In different electrical equipments shown in Table 1 below, test comprises the set of cells of electrolyte 113 and 115.Compare comprising the performance testing electrolytical set of cells with comprising the electrolytical set of cells of control.
Table 1
As shown in table 1, though the hydraulic performance decline that there occurs under high discharge rate (such as DSC test), the set of cells comprising electrolyte 113 and 115 shows the performance improved under other speed (rate).Set of cells for comprising electrolyte 113 is especially true.
Believe and these results are attributed to the sulfolane all comprised in both electrolyte 113 and 115 at least partially.Sulfolane has the boiling point (285 DEG C) higher than other solvents (that is, about 100 DEG C) controlled in electrolyte.As a result, compared with having the electrolytical battery of control, the loss in weight of the battery at high temperature memory period comprising sulfolane is much smaller.Table 2 discloses and stores after one to ten day the electrolytical loss in weight of the difference (wt.%) of test at 71 DEG C in a vacuum.
Table 2
| Storage (natural law) | Control electrolyte | #113(%) | #115(%) |
| 1 | 0.0256 | 0.0133 | 0.0099 |
| 2 | 0.0477 | 0.0248 | 0.0238 |
| 3 | 0.066 | 0.0354 | 0.0302 |
| 4 | 0.0873 | 0.0317 | 0.0286 |
| 5 | 0.1042 | 0.0385 | 0.043 |
| 6 | 0.1305 | 0.0462 | 0.046 |
| 7 | 0.1509 | 0.0557 | 0.0532 |
| 8 | 0.1722 | 0.0592 | 0.0625 |
| 9 | 0.1926 | 0.0669 | 0.0738 |
| 10 | 0.2102 | 0.0724 | 0.0825 |
Also believing that, electrolyte 113 shows reliability more better than control electrolyte, this is because the flash-point of electrolyte 113 (flashpoint) is higher than the flash-point controlling electrolyte #45.
Example 11
Example 11 discloses different extruding and impact test that sample AA set of cells is carried out.
Extruding method of testing
The pretreated set of cells for the following parameters shown in table 3 is performed extruding test (the required test of UL1642 and/or ANSI18.3 test).
Table 3
Set of cells is extruded between two flat surfaces according to following process: the first make contact that is squeezed in of set of cells is sentenced the speed of about 1.5cm/s and is carried out gradually, carries out the preparation of voltage measurement during this period.Power for extruding is applied by hydraulic cylinder, and this hydraulic cylinder has the piston of 1.25 inches of (32mm) diameters.The persistently extruding to set of cells, until reaching first in three options:
1. the power applied reaches 13KN(and reaches the pressure of 17MPa).The power applied at this point is 3,000lbs(13KN)；Or
2. the voltage of set of cells declines at least 100mV；Or
3. set of cells has deformed 50% or more than its original thickness.
Once obtain maximum pressure, voltage decline 100mV or more or battery to have deformed at least 50% than its original thickness, this pressure is released.
Set of cells is extruded in the way of its longitudinal axis is parallel with the flat surfaces of extrusion equipment, and is perpendicular to the power that this longitudinal axis applies to extrude.
Each test set of cells is only once extruded.Then test sample is carried out the observation of extra six hours.
Impact test method
The pretreated set of cells for the following parameters shown in table 4 is performed impact test (UL1642 tests, and/or ANSI18.3 tests, and/or UN38.3 tests).
Table 4
Before starting impact test, the set of cells of each pretreatment is performed x-radial imaging, to determine internal battery pack winding initial void volume.
Figure 12 illustrates the equipment for impact test.Impact test carries out in steel striker chamber 24.Set of cells 28 is placed on the flat surfaces in chamber 24.Then the horizontal stripe (bar) 30 of 5/8 inch diameter is arranged through the center of set of cells 28.Then pass through operating weight supporting rope 20, the counterweights 26 of 20 pounds are dropped to set of cells 28 from the height of two feet by sealing pipe 22.
Set of cells parallel with flat surfaces by its longitudinal axis and with through (lieacross) test sample center 5/8 inch of (15.8mm) diameter curved surface axis oriented normal in the way of be knocked.Each Sample Cell group is only carried out single impact.
The failure criterion of set of cells sample is as follows: during testing the temperature in chamber not should more than 170 DEG C and set of cells sample should not explode or catch fire (in six hours tested).
Extruding and impact test result
It is battery size AA set of cells for the set of cells sample extruded with impact test.Describe the electrode size size according to the disclosure, reference battery design and new exemplary design in table 5.
Table 5
| Electrode size | Reference battery | Exemplary battery design 14--> | |
| Negative electrode | Length (mm) | 310 | 287 |
| Width (mm) | 40.5 | 39 | |
| Thickness (mm) | 0.165 | 0.165 | |
| Anode | Length (mm) | 280 | 258 |
| Width (mm) | 39 | 37 | |
| Thickness (mm) | 0.180 | 0.180 | |
| Dividing plate | Width (mm) | 44 | 44 |
| Thickness (mm) | 0.02 | 0.02 | |
| Voidage (%) | 26.7% | 34.0% |
As shown in table 5, tested battery includes different electrode sizes, and it is used for optimizing voidage.Meanwhile, during partial discharge, carry out other relevant adjustment change to minimize voidage.After optimizing electrode size and battery configuration, design satisfied or overproof industry impact test and extruding test according to the exemplary battery of the disclosure.
-----
In view of above-mentioned, it can be seen that some advantages of the disclosure can be obtained, and obtain other beneficial outcomes.Owing to said process and complex can carry out various amendment without deviating from the scope of the present disclosure, all the elements that comprise in above description and illustrated in the accompanying drawings are intended to be interpreted exemplary rather than restrictive.
When introducing key element or various version, embodiment or its aspect of the disclosure, article " ", " being somebody's turn to do ", " described " are intended to indicate that one or more key element.Term " comprises ", " including ", " having " are intended to inclusive, and the key element existed except listed key element that expresses possibility.The use of the term (such as " top ", " bottom ", " side " etc.) of expression specific orientation is for the ease of describing, it is not required that any specific orientation of described entry.
Claims (7)
1. an electrochemical primary cells, including:
Battery case；
Comprise the anode of lithium；
Comprising the negative electrode of active material of cathode, described active material of cathode comprises ferrous disulfide；
Dividing plate, it is arranged between described anode and described negative electrode；And
Nonaqueous electrolyte, its with described anode, negative electrode and dividing plate communication, wherein, described electrolyte comprises solvent, dissolve wherein salt and pH adjuster, wherein, described pH adjuster is the inorganic additive selected from ammonium carbonate and ammonium hydrogen carbonate or its combination to exist by the amount of 0.1% to the 5.0% of described electrolytical weight；And wherein, to comprise 3, the 5-dimethyl of the dioxolanes of 55 volume % to 70 volume %, the sulfolane of 30 volume % to 45 volume % and 0.1 volume % to 0.5 volume % different for described solventThe mixture of azoles.
2. electrochemical primary cells as claimed in claim 1, wherein, described salt is selected from lithium iodide, lithium nitrate, double; two (fluoroform sulphonyl) imine lithium and its mixture.
3. electrochemical primary cells as claimed in claim 1, wherein, described electrolyte has the water content less than 50ppm.
4. electrochemical primary cells as claimed in claim 1, wherein, described salt comprises double; two (fluoroform sulphonyl) imine lithiums of 0.75 to 1M.
5. electrochemical primary cells as claimed in claim 1, wherein, described battery also includes gasket seal material, and described gasket seal material comprises polypropylene and Ethylene-Propylene-Diene monomer copolymer.
6. electrochemical primary cells as claimed in claim 1, wherein, described battery also includes positive temperature coefficient (PTC) device.
7. electrochemical primary cells as claimed in claim 1, wherein, described salt is lithium nitrate.
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| CN1830045A (en) * | 2003-07-29 | 2006-09-06 | 松下电器产业株式会社 | Aluminum electrolytic capacitor |
| CN101088185A (en) * | 2004-12-22 | 2007-12-12 | 永备电池有限公司 | High discharge capacity lithium battery |
| CN102024953A (en) * | 2010-11-06 | 2011-04-20 | 广州市鹏辉电池有限公司 | Positive electrode material of lithium-iron disulfide battery and battery |
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| US5290414A (en) | 1992-05-15 | 1994-03-01 | Eveready Battery Company, Inc. | Separator/electrolyte combination for a nonaqueous cell |
| JP2001526451A (en) * | 1997-12-10 | 2001-12-18 | ミネソタ マイニング アンド マニュファクチャリング カンパニー | Bis (perfluoroalkylsulfonyl) imide surfactant salts in electrochemical systems |
| US20050112462A1 (en) | 2003-11-21 | 2005-05-26 | Marple Jack W. | High discharge capacity lithium battery |
| US7196137B2 (en) * | 2002-02-08 | 2007-03-27 | Teknor Apex Company | Polymer compositions |
| US8124274B2 (en) * | 2003-11-21 | 2012-02-28 | Eveready Battery Company, Inc. | High discharge capacity lithium battery |
| US20090191466A1 (en) | 2006-07-27 | 2009-07-30 | The Gillette Company | Battery |
| US20090214950A1 (en) | 2008-02-22 | 2009-08-27 | Bowden William L | Lithium cell |
| US20100203370A1 (en) | 2009-02-12 | 2010-08-12 | Michael Pozin | Lithium cell with iron disulfide cathode |
| US8048562B2 (en) * | 2009-03-27 | 2011-11-01 | The Gillette Company | Lithium cell with improved iron disulfide cathode |
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| CN1830045A (en) * | 2003-07-29 | 2006-09-06 | 松下电器产业株式会社 | Aluminum electrolytic capacitor |
| CN101088185A (en) * | 2004-12-22 | 2007-12-12 | 永备电池有限公司 | High discharge capacity lithium battery |
| CN102024953A (en) * | 2010-11-06 | 2011-04-20 | 广州市鹏辉电池有限公司 | Positive electrode material of lithium-iron disulfide battery and battery |
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